TWI572282B - Pesticidal mixtures including spiroheterocyclic pyrrolidine diones - Google Patents

Description

Pesticide mixture containing spiroheteroprolidinedione

The present invention relates to mixtures of pesticidal active ingredients and to methods of using such mixtures to control insects, mites, nematodes or molluscs.

Certain spiroheteropyrrolidinediones have insecticidal activity as disclosed in WO 2009/049851, WO 2010/063670, and WO 10/066780.

The present invention provides a pesticidal mixture comprising a mixture of component A and component B as an active ingredient, wherein component A is a compound of formula (I) Where Q is i or ii

X, Y and Z are each independently C _1-4 alkyl, C _1-4 haloalkyl, C _1-4 alkoxy, C _1-4 haloalkoxy, halogen; m and n are independently of each other 0, 1, 2 or 3 and m+n is 0, 1, 2 or 3; G is hydrogen, metal, ammonium, ruthenium or latentating group; R is hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl; A hydrogen, C _1-4 alkyl, C _1-4 haloalkyl, C _2-4 alkenyl, C _2-4 haloalkenyl, C _1-4 alkoxy (C _1-4 )alkyl, C _1-4 haloalkoxy(C _1-4 )alkyl, C _1-4 alkoxy(C _1-4 )alkoxy(C _1-4 )alkyl , tetrahydrofuranyl, tetrahydropyranyl; and or an agrochemically acceptable salt or N-oxide thereof; and component B is selected from at least one of the following: a) pymetrozine; b) Pyrethroid selected from the group consisting of cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin ; c). A macrolide selected from the group consisting of abamectin, emamectin benzoate, and spinetoram; d) a diamine selected from the group consisting of the following Composition: chlorantraniliprole; Rynaxypyr® and cyantraniliprole; Cyazypyr®; e) thiamethoxam; f). sulfoxaflorin; g) cyenopyrafen; in the compound of formula A having component (I), each alkyl moiety, either alone or as part of a larger group, is linear or branched and is For example, methyl, ethyl, n-propyl, n-butyl, isopropyl, secondary butyl, isobutyl, and tertiary butyl.

The alkoxy group preferably has a chain length of preferably from 1 to 4 carbon atoms. Alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, di-butoxy and tert-butoxy. The groups may be part of a larger group such as an alkoxyalkyl group and an alkoxyalkoxyalkyl group. The alkoxyalkyl group is preferably a chain length having 1 to 4 carbon atoms. Alkoxyalkyl, such as methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl or isopropoxy methyl.

Halogen is usually fluorine, chlorine, bromine or iodine. Accordingly, it is also applicable to the combination of halogen with other meanings such as haloalkyl or haloalkoxy.

The haloalkyl and haloalkoxy groups preferably have a chain length of from 1 to 4 carbon atoms. Haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl , 2-chloroethyl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-tri Chloroethyl; preferred are trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl, and dichlorofluoromethyl. Haloalkoxy, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chloromethoxy, dichloromethoxy, trichloromethoxy, 2,2,2-trifluoroethyl Oxyl, 2-fluoroethoxy, 2-chloroethoxy, pentafluoroethoxy, 1,1-difluoro-2,2,2-trichloroethoxy, 2,2,3,3- Tetrafluoroethoxy and 2,2,2-trichloroethoxy; preferably trichloromethoxy, difluorochloromethoxy, difluoromethoxy, trifluoromethoxy and dichlorofluoro Methoxy.

The latent groups G are selected to allow removal of the group by one or a combination of biochemical, chemical or physical methods before, during or after application to the treatment zone or plant to provide a G system therein Hydrogen, having the compound of formula (I). Examples of such methods include enzyme digestion, Chemical hydrolysis and photolysis. Compounds having such groups G may provide certain advantages, such as improved permeability of the stratum corneum of treated plants, improved tolerance of crops, inclusion of other herbicides, herbicide safeners, plant growth regulation The compatibility or stability of the formulated mixture of the agent, fungicide or insecticide is improved, or leaching in the soil is reduced.

Such latent groups are known in the art, for example, in WO 08/071405, WO 09/074314, WO 09/049851, WO 10/063670, and WO 10/066780.

In an embodiment, the latent group is selected from the group consisting of -C(=O)-R ^a and -C(=O)-OR ^b ; wherein R ^a is selected from hydrogen, C ₁ -C ₁₂ alkyl , C ₂ -C ₁₂ alkenyl, C ₂ -C ₁₂ alkynyl, C ₁ -C ₁₀ haloalkyl and R ^b is selected from C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₂ - C ₁₂ alkynyl and C ₁ -C ₁₀ haloalkyl. Specifically, R ^a and R ^b are selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, and tri- Butyl, vinyl and propenyl, for example 2-propen-1-yl.

Preferably, G is hydrogen, a metal (preferably an alkali metal or alkaline earth metal), or an ammonium or sulfonium group, of which hydrogen is particularly preferred.

Depending on the nature of the substituents, the compounds of formula (I) can exist in different isomeric forms. When G is hydrogen, for example, a compound of formula (I) can exist in different tautomeric forms:

The present invention encompasses all isomers as well as tautomers and mixtures thereof in all ratios. Also, when the substituent includes a double bond, the cis and trans isomers may be present. Such isomers are also within the scope of the claimed compounds of formula (I).

The invention further relates to agriculturally acceptable salts which are capable of forming the salts of the compounds of formula (I) with transition metals, alkali metals and alkaline earth metal bases, amines, quaternary ammonium bases or tertiary sulfonamides.

Among the transition metal, alkali metal and alkaline earth metal salt formations, particular mention should be made of hydroxides of copper, iron, lithium, sodium, potassium, magnesium and calcium, and preferably sodium. With potassium hydroxide, bicarbonate and carbonate.

Examples of amines suitable for the formation of ammonium salts include ammonia and primary, secondary and tertiary C ₁ -C ₁₈ alkylamines, C ₁ -C ₄ hydroxyalkylamines and C ₂ -C ₄ alkoxyalkylamines, For example, methylamine, ethylamine, n-propylamine, isopropylamine, four butylamine isomers, n-pentylamine, isoamylamine, hexylamine, heptylamine, octylamine, decylamine, decylamine, pentaamine, sixteen Amine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylamine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethyl Heptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n-propylamine, di-isopropylamine, di-n-butylamine, di-n-pentylamine, di-isoprene Amine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allyl Amine, n-but-2-enamine, n-pent-2-enamine, 2,3-dimethylbut-2-enamine, dibutyl-2-enamine, n-hex-2-enamine , propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, tri-iso-propylamine, tri-n-butylamine, tri-iso-butylamine, tri-di-butylamine , tri-n-pentylamine, methoxyethylamine, and ethoxyethylamine; heterocyclic amines, such as pyridine, quinoline, isoquinoline, Porphyrin, piperidine, pyrrolidine, indoline, Pyridine and azide; primary arylamines such as aniline, methoxyaniline, ethoxyaniline, o-, m- and p-toluidine, phenylenediamine, benzidine, naphthylamine, and o-, m-- Para-chloroaniline; but especially triethylamine, isopropylamine and diisopropylamine.

Preferred quaternary ammonium bases suitable for salt formation are, for example, of the formula [N(R _a R _b R _c R _d )]OH, wherein R _a , R _b , R _c and R _d are each independently hydrogen or C ₁ - C ₄ alkyl. Further suitable tetraalkylammonium bases having other anions can be obtained by, for example, anion exchange reaction.

Preferred tertiary sulfonium bases suitable for salt formation are, for example, of the formula [SR _e R _f R _g ]OH, wherein R _e , R _f and R _g are, independently of each other, a C ₁ -C ₄ alkyl group. Trimethylhydrazine hydroxide is particularly preferred. Suitable sulfonium bases can be obtained by reacting a thioether (especially a dialkyl sulfide) with an alkyl halide and then converting it to a suitable base, such as a hydroxide, by an anion exchange reaction.

The compounds of the present invention can be prepared by a variety of methods as described in detail in, for example, WO 09/049851, WO 10/063670, and WO 10/066780.

It should be understood that in those compounds of formula (I) wherein G is a metal, ammonium or ruthenium as described above and represents a cation as it is, the corresponding negative charge largely crosses the OC=CC=O unit. Non-localized.

The compounds of formula (I) according to the invention also include hydrates which may form during the formation of the salt.

Preferably, in the compound of formula (I), the substituent R is hydrogen, C _1-4 alkyl, C _1-4 haloalkyl, specifically methyl, ethyl, isopropyl, n-propyl. Base, tertiary butyl, secondary butyl, isobutyl or n-butyl.

Preferably, when m+n is 1, 2 or 3, especially when m+n is 1 or 2, X, Y and Z are independently selected from each other from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or halogen, in particular methyl, ethyl, isopropyl, n-propyl, methoxy, fluoro, bromo or chloro.

Alternatively, when m+n is 1, 2 or 3, particularly when m+n is 1 or 2, Y and Z independently of each other represent C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy , halogen, specifically methyl, ethyl, isopropyl, n-propyl, methoxy, fluorine, chlorine, bromine.

In a specific embodiment, in the compound of formula (I), when m is 1, Y is in the ortho position and X and Y are each independently selected from the group consisting of methyl, Base, isopropyl and n-propyl.

In another embodiment, it is preferred to combine with the preceding embodiments, wherein in the compound of formula (I), when n is 1, Z is in the para position and is selected from the group consisting of the group It consists of fluorine, bromine, and chlorine, methyl, ethyl, isopropyl, and n-propyl groups. Preferably, Z is methyl, fluorine, bromine and chlorine. More preferably, Z is chlorine.

In another embodiment, wherein, in the compound of formula (I), when m and n are each 1, Y is in the ortho position and X and Y are independently selected from the group consisting of : methyl and ethyl, and Z is in the para position and is selected from the group consisting of fluorine, bromine and chlorine. Preferably, X and Y are each in the ortho position and are methyl, and preferably, the Z system is in the para position and is chlorine.

In the compound of the formula (I), the substituent A is preferably hydrogen, C _1-4 alkyl, C _1-4 haloalkyl, C _2-4 alkenyl, C _1-4 alkoxy (C) _1-4 ) alkyl, C _1-4 alkoxy (C _1-4 ) alkoxy (C _1-4 ) alkyl, tetrahydrofuranyl, tetrahydropyranyl, specifically methyl, ethyl, positive Propyl, isopropyl, n-butyl, isobutyl, secondary butyl and tert-butyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-difluoroethyl, 2-fluoroethyl, allyl, methoxymethyl, ethoxymethyl, methoxyethyl, methoxypropyl, methoxyethoxymethyl, methoxymethoxy B Base, tetrahydrofuran-2-yl, tetrahydropyran-2-yl, tetrahydrofuran-3-yl, tetrahydropyran-4-yl.

Among the compounds of the formula (I), Q is preferably (i).

In one embodiment, when Q is (i), A is preferably hydrogen.

In another embodiment, when Q is (i), the A is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl Base, secondary butyl, tert-butyl, methoxymethyl, ethoxymethyl and methoxyethyl. Preferably, when Q is (i), A is a methyl group.

In another embodiment, when Q is (ii), the A is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, Isobutyl, tert-butyl, methoxymethyl, ethoxymethyl, methoxyethyl, methoxypropyl, tetrahydrofuran-2-yl, tetrahydropyran-2-yl, tetrahydrofuran- 3-Based and tetrahydropyran-4-yl. Preferably, when Q is (ii), A is hydrogen, methyl, ethyl, methoxymethyl and tetrahydrofuran-2-yl.

In another preferred group of compounds of formula (I), R is one of hydrogen, methyl, ethyl or trifluoromethyl, X is methyl, ethyl or methoxy, and Y and Z are independent of each other. The ground is methyl, ethyl, methoxy, fluoro, chloro or bromo, G is hydrogen or -(C=O)CO-CH ₂ CH ₃ and A has the meanings specified above.

In a particularly preferred group of compounds of formula (I), R is methyl or ethyl, X is methyl, ethyl, methoxy, fluoro, bromo or chloro, and Y and Z are independently methyl. Ethyl, methoxy, fluoro, chloro or bromo, G is hydrogen or -(C=O)CO-CH ₂ CH ₃ and A has the meanings specified above.

In a more preferred group of compounds of formula (I), R is methyl or ethyl, X is methyl, ethyl, methoxy, fluoro, bromo or chloro, and Y and Z are each independently methyl. , ethyl, methoxy, fluoro, chloro, bromo, G-hydrogen or -(C=O)CO-CH ₂ CH ₃ and A is hydrogen, methyl, ethyl, isopropyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-difluoroethyl, 2-fluoroethyl, tetrahydrofuran-2-ylmethyl, tetrahydropyran-2-ylmethyl, tetrahydrofuran-3-yl Methyl, tetrahydropyran-3-ylmethyl, tetrahydropyran-4-ylmethyl, allyl, methoxymethyl, ethoxymethyl, methoxyethyl, methoxy Propyl, methoxyethoxymethyl, methoxymethoxyethyl, tetrahydrofuran-2-yl, tetrahydropyran-2-yl, tetrahydrofuran-3-yl or tetrahydropyran-4-yl .

In another preferred group of compounds of formula (I), R is methyl, X is methyl or methoxy, and Y and Z are, independently of each other, methyl, ethyl, methoxy, chloro or bromo. , G is hydrogen, methoxycarbonyl or propyleneoxycarbonyl or -(C=O)CO-CH ₂ CH ₃ and A is hydrogen, methyl, ethyl, methoxymethyl, tetrahydrofuran-2-yl or Tetrahydrofuran-3-yl.

In another preferred group of compounds of formula (I), Q is (i), m is 1, n is 1, X is methyl, Y is in the ortho position and is methyl, Z is in the para position Further, it is chlorine, G-based hydrogen or -(C=O)CO-CH ₂ CH ₃ , A-based methyl group, and R-based methyl group.

In another preferred group of compounds of formula (I), Q is (i), m is 1, n is 1, X is methyl, Y is in the ortho position and is methyl, Z is in the para position Further, it is chlorine, G-based hydrogen or -(C=O)CO-CH ₂ CH ₃ , A-based hydrogen, and R-based methyl group.

Compounds of formula (I) according to the following table can be prepared according to the methods disclosed in the art mentioned above.

Table 1: This table discloses 107 compounds T1.001 to T1.107 having the subformula (Ia): Wherein R is CH ₃ , A is CH ₃ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined below:

Table 2: This table discloses 107 compounds T2.001 to T2.107 having the formula (Ia), wherein R is CH ₃ , A is CH ₂ CH ₃ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 3: This table discloses 107 compounds T3.001 to T3.107 having the formula (Ia), wherein R is CH ₃ , A is nC ₃ H ₇ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 4: This table discloses 107 compounds T4.001 to T4.107 having the formula (Ia), wherein R is CH ₃ , A is iC ₃ H ₇ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 5: This table discloses 107 compounds T5.001 to T5.107 having the formula (Ia), wherein R is CH ₃ , A is nC ₄ H ₉ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 6: This table discloses 107 compounds T6.001 to T6.107 having the formula (Ia), wherein R is CH ₃ , A is iC ₄ H ₉ , G is hydrogen and R _a , R _b , R _c and R _d is as defined in Table 1.

Table 7: This table discloses 107 compounds T7.001 to T7.107 having the formula (Ia), wherein R is CH ₃ , A is tC ₄ H ₉ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 8: This table discloses 107 compounds T8.001 to T8.107 having the formula (Ia), wherein R is CH ₃ , A is 2,2-(CH ₃ ) ₂ -propyl, G-based-(C =O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 9: This table discloses 107 compounds T9.001 to T9.107 having the formula (Ia) wherein R is CH ₃ , A is allyl, G is -(C=O)CO-CH ₂ CH ₃ And R _a , R _b , R _c and R _d are as defined in Table 1.

Table 10: This table discloses 107 compounds of formula (Ia) T10.001 to T10.107, where R is CH ₃ , A is CH ₂ -CH=C(CH ₃ ) ₂ , G is - (C= O) CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 11: This table discloses 107 compounds T11.001 to T11.107 having the formula (Ia), wherein R is CH ₃ , A is CH ₂ -CH=C(Cl) ₂ , G is -(C=O CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 12: This table discloses 107 compounds T12.001 to T12.107 having the formula (Ia), wherein R is CH ₃ , A is CH ₂ OCH ₃ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 13: This table discloses 107 compounds T13.001 to T13.107 having the formula (Ia), wherein R is CH ₃ , A is CH ₂ OCH ₂ CH ₃ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 14: This table discloses 107 compounds T14.001 to T14.107 of formula (Ia), wherein R is CH ₃ , A is CH ₂ CH ₂ OCH ₃ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 15: This table discloses 107 compounds T15.001 to T15.107 having the formula (Ia), wherein R is CH ₃ , A is CH ₂ OCH ₂ CH ₂ OCH ₃ , G is -(C=O)CO -CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 16: This table discloses 107 compounds T16.001 to T16.107 having the formula (Ia), wherein R is CH ₃ , A is CH ₂ CH ₂ OCH ₂ OCH ₃ , G is -(C=O)CO -CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 17: This table discloses 107 compounds T17.001 to T17.107 having the formula (Ia) wherein R is CH ₃ , A is tetrahydrofuran-2-yl, G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 18: This table discloses 107 compounds of formula (Ia) T18.001 to T18.107, wherein R is CH ₃ , A is tetrahydrofuran-3-yl, G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 19: This table discloses 107 compounds T19.001 to T19.107 having the formula (Ia) wherein R is CH ₃ , A is tetrahydropyran-2-yl, G is -(C=O)CO -CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 20: This table discloses 107 compounds of formula (Ia) T20.001 to T20.107, wherein R is CH ₃ , A is tetrahydropyran-4-yl, G-system-(C=O)CO -CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 21: This table discloses 107 compounds T21.001 to T21.107 having the formula (Ia) wherein R is CH ₃ , A is CH ₂ CH ₂ F, and G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 22: This table discloses 107 compounds T22.001 to T22.107 having the formula (Ia) wherein R is CH ₃ , A is CH ₂ CHF ₂ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 23: This table discloses 107 compounds T23.001 to T23.107 having the formula (Ia) wherein R is CH ₃ , A is CH ₂ CF ₃ , G is hydrogen and R _a , R _b , R _c and R _d is as defined in Table 1.

Table 24: This table discloses 107 compounds T24.001 to T24.107 having the formula (Ia), wherein R is hydrogen, A is CH ₃ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 25: This table discloses 107 compounds of the formula (Ia) T25.001 to T25.107, wherein R is hydrogen, A is CH ₂ CH ₃ , G is -(C=O)CO-CH ₂ CH ₃ And R _a , R _b , R _c and R _d are as defined in Table 1.

Table 26: This table discloses 107 compounds of formula (Ia) T26.001 to T26.107, wherein R is hydrogen, A is iC ₃ H ₇ , G is -(C=O)CO-CH ₂ CH ₃ And R _a , R _b , R _c and R _d are as defined in Table 1.

Table 27: This table discloses 107 compounds T27.001 to T27.107 having the formula (Ia), wherein R is hydrogen, A is CH ₂ OCH ₃ , G is -(C=O)CO-CH ₂ CH ₃ And R _a , R _b , R _c and R _d are as defined in Table 1.

Table 28: This table discloses 107 compounds of formula (Ia) T28.001 to T28.107, wherein R is hydrogen, A is CH ₂ CH ₂ OCH ₃ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 29: This table discloses 107 compounds T29.001 to T29.107 having the formula (Ia) wherein R is hydrogen, A is CH ₂ OCH ₂ CH ₂ OCH ₃ , G is -(C=O)CO- CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 30: This table discloses 107 compounds of formula (Ia) T30.001 to T30.107, wherein R is hydrogen, A is CH ₂ CH ₂ OCH ₂ OCH ₃ , G is -(C=O)CO- CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 31: This table discloses 107 compounds T31.001 to T31.107 having the formula (Ia) wherein R is hydrogen, A is CH ₂ CHF ₂ , G is -(C=O)CO-CH ₂ CH ₃ And R _a , R _b , R _c and R _d are as defined in Table 1.

Table 32: This table discloses 107 compounds of formula (Ia) T32.001 to T32.107, wherein R is hydrogen, A is CH ₂ CF ₃ , G is -(C=O)CO-CH ₂ CH ₃ And R _a , R _b , R _c and R _d are as defined in Table 1.

Table 33: This table discloses 107 compounds of formula (Ia) T33.001 to T33.107, wherein R is CH ₂ CH ₃ , A is CH ₃ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 34: This table discloses 107 compounds of formula (Ia) T34.001 to T34.107, wherein R is CH ₂ CH ₃ , A is CH ₂ CH ₃ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 35: This table discloses 107 compounds T35.001 to T35.107 having the formula (Ia), wherein R is CH ₂ CH ₃ , A is iC ₃ H ₇ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 36: This table discloses 107 compounds T36.001 to T36.107 having the formula (Ia), wherein R is CH ₂ CH ₃ , A is CH ₂ OCH ₃ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 37: This table discloses 107 compounds T37.001 to T37.107 having the formula (Ia), wherein R is CH ₂ CH ₃ , A is CH ₂ CH ₂ OCH ₃ , G is -(C=O)CO -CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 38: This table discloses 107 compounds of formula (Ia) T38.001 to T38.107, wherein R is CH ₂ CH ₃ , A is CH ₂ OCH ₂ CH ₂ OCH ₃ , G is - (C=O CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 39: This table discloses 107 compounds of formula (Ia) T39.001 to T39.107, where R is CH ₂ CH ₃ , A is CH ₂ CH ₂ OCH ₂ OCH ₃ , G is - (C=O CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 40: This table discloses 107 compounds of formula (Ia) T40.001 to T40.107, where R is CH ₂ CH ₃ , A is CH ₂ CHF ₂ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 41: This table discloses 107 compounds T41.001 to T41.107 having the formula (Ia), wherein R is CH ₂ CH ₃ , A is CH ₂ CF ₃ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 42: This table discloses 107 compounds T42.001 to T42.107 having the formula (Ia) wherein R is CH ₃ , A is methoxypropyl, G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 43: This table discloses 107 compounds of formula (Ia) T43.001 to T43.107, wherein R is H, A is methoxypropyl, G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 44: This table discloses 107 compounds of formula (Ia) T44.001 to T44.107, wherein R is CH ₂ CH ₃ , A is methoxypropyl, G is -(C=O)CO- CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1.

Table 1ii: This table discloses 107 compounds T1ii.001 to T1ii.107 having the subformula (Ib): Wherein R is CH ₃ , A is hydrogen, G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined below:

Table 2ii: This table discloses 107 compounds T2ii.001 to T2ii.107 having the formula (Ib), wherein R is CH ₃ , A is CH ₃ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 3ii: This table discloses 107 compounds T3ii.001 to T3ii.107 having the formula (Ib), wherein R is CH ₃ , A is CH ₂ CH ₃ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 4ii: This table discloses 107 compounds T4ii.001 to T4ii.107 having the formula (Ib), wherein R is CH ₃ , A is nC ₃ H ₇ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 5ii: This table discloses 107 compounds T5ii.001 to T5ii.107 having the formula (Ib), wherein R is CH ₃ , A is iC ₃ H ₇ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 6ii: This table discloses 107 compounds T6ii.001 to T6ii.107 having the formula (Ib), wherein R is CH ₃ , A is nC ₄ H ₉ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 7ii: This table discloses 107 compounds T7ii.001 to T7ii.107 having the formula (Ib), wherein R is CH ₃ , A is iC ₄ H ₉ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 8ii: This table discloses 107 compounds T8ii.001 to T8ii.107 having the formula (Ib), wherein R is CH ₃ , A is tC ₄ H ₉ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 9ii: This table discloses 107 compounds T9ii.001 to T9ii.107 having the formula (Ib), wherein R is CH ₃ , A is 2,2-(CH ₃ ) ₂ -propyl, G-based-(C =O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 10ii: This table discloses 107 compounds T10ii.001 to T10ii.107 having the formula (Ib) wherein R is CH ₃ , A is allyl, G is -(C=O)CO-CH ₂ CH ₃ And R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 11ii: This table discloses 107 compounds T11ii.001 to T11ii.107 having the formula (Ib), wherein R is CH ₃ , A is CH ₂ -CH=C(CH ₃ ) ₂ , G is - (C= O) CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 12ii: This table discloses 107 compounds of formula (Ib) T12ii.001 to T12ii.107, where R is CH ₃ , A is CH ₂ -CH=C(Cl) ₂ , G is - (C=O CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 13ii: This table discloses 107 compounds T13ii.001 to T13ii.107 having the formula (Ib), wherein R is CH ₃ , A is CH ₂ OCH ₃ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 14ii: This table discloses 107 compounds of formula (Ib) T14ii.001 to T14ii.107, where R is CH ₃ , A is CH ₂ OCH ₂ CH ₃ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 15ii: This table discloses 107 compounds T15ii.001 to T15ii.107 having the formula (Ib), wherein R is CH ₃ , A is CH ₂ CH ₂ OCH ₃ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 16ii: This table discloses 107 compounds of formula (Ib) T16ii.001 to T16ii.107, where R is CH ₃ , A is CH ₂ OCH ₂ CH ₂ OCH ₃ , G is -(C=O)CO -CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 17ii: This table discloses 107 compounds T17ii.001 to T17ii.107 having the formula (Ib) wherein R is CH ₃ , A is tetrahydrofuran-2-yl, G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 18ii: This table discloses 107 compounds T18ii.001 to T18ii.107 having the formula (Ib) wherein R is CH ₃ , A is tetrahydrofuran-3-yl, G is hydrogen and R _a , R _b , R _c And R _d is as defined in Table 1ii.

Table 19ii: This table discloses 107 compounds of formula (Ib) T19ii.001 to T19ii.107, wherein R is CH ₃ , A is tetrahydropyran-2-yl, G-system-(C=O)CO -CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 20ii: This table discloses 107 compounds T20ii.001 to T20ii.107 having the formula (Ib) wherein R is CH ₃ , A is tetrahydropyran-4-yl, G-system-(C=O)CO -CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 21ii: This table discloses 107 compounds T21ii.001 to T21ii.107 having the formula (Ib), wherein R is CH ₃ , A is CH ₂ CHF ₂ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 22ii: This table discloses the 107 compounds of formula (Ib) to a T22ii.001 T22ii.107, wherein R type hydrogen, A Department of hydrogen, G Department - (C = O) CO- CH 2 CH 3 and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 23ii: This table discloses 107 compounds T23ii.001 to T23ii.107 having the formula (Ib) wherein R is hydrogen, A is CH ₃ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 24ii: This table discloses 107 compounds of formula (Ib) T24ii.001 to T24ii.107, where R is hydrogen, A is CH ₂ OCH ₃ , G is -(C=O)CO-CH ₂ CH ₃ And R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 25ii: This table discloses 107 compounds T25ii.001 to T25ii.107 having the formula (Ib), wherein R is hydrogen, A is CH ₂ CH ₂ OCH ₃ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 26ii: This table discloses 107 compounds of formula (Ib) T26ii.001 to T26ii.107, where R is CH ₂ CH ₃ , A is hydrogen, G is -(C=O)CO-CH ₂ CH ₃ And R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 27ii: This table discloses 107 compounds T27ii.001 to T27ii.107 having the formula (Ib), wherein R is CH ₂ CH ₃ , A is CH ₃ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 28ii: This table discloses 107 compounds of formula (Ib) T28ii.001 to T28ii.107, where R is CH ₂ CH ₃ , A is CH ₂ OCH ₃ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 29ii: This table discloses 107 compounds of formula (Ib) T29ii.001 to T29ii.107, where R is CH ₂ CH ₃ , A is CH ₂ CH ₂ OCH ₂ , G is -(C=O)CO -CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 30ii: This table discloses 107 compounds T30ii.001 to T30ii.107 having the formula (Ib), wherein R is CH ₃ , A is CH ₂ CH ₂ CH ₂ OCH ₃ , G is -(C=O)CO -CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 31ii: This table discloses 107 compounds T31ii.001 to T31ii.107 having the formula (Ib), wherein R is hydrogen, A is CH ₂ CH ₃ , G is -(C=O)CO-CH ₂ CH ₃ And R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 32ii: This table discloses 107 compounds T32ii.001 to T32ii.107 having the formula (Ib) wherein R is hydrogen, A is allyl, G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 33ii: This table discloses 107 compounds of formula (Ib) T33ii.001 to T33ii.107, wherein R is hydrogen, A is tetrahydrofuran-2-yl, G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 34ii: This table discloses 107 compounds of formula (Ib) T34ii.001 to T34ii.107, wherein R is hydrogen, A is tetrahydropyran-2-yl, G is -(C=O)CO- CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 35ii: This table discloses 107 compounds T35ii.001 to T35ii.107 having the formula (Ib), wherein R is CH ₂ CH ₃ , A is CH ₂ CH ₃ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 36ii: This table discloses 107 compounds of formula (Ib) T36ii.001 to T36ii.107, wherein R is CH ₂ CH ₃ , A is allyl, G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 37ii: This table discloses 107 compounds of formula (Ib) T37ii.001 to T37ii.107, wherein R is CH ₂ CH ₃ , A is tetrahydrofuran-2-yl, G is -(C=O)CO- CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1ii.

Table 38ii: This table discloses 107 compounds of formula (Ib) T38ii.001 to T38ii.107, wherein R is CH ₂ CH ₃ , A is tetrahydropyran-2-yl, G-system-(C=O CO-CH ₂ CH ₃ and R _a , R _d , R _c and R _d are as defined in Table 1ii.

Table 1iii: This table discloses 87 compounds T1iii.001 to T1iii.87 having the subformula (Ic): Wherein R is CH ₃ , G is -(C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined below:

Table 2iii: This table discloses 87 compounds T2iii.001 to T2iii.87 having the formula (Ic) wherein R is CH ₂ CH ₃ , R ₁ , R ₂ , R ₃ and R ₄ are hydrogen, G-system-( C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1iii.

Table 3iii: This table discloses 87 compounds T3iii.001 to T3iii.87 having the formula (Ic) wherein R is nC ₃ H ₇ , R ₁ , R ₂ , R ₃ and R ₄ are hydrogen, G-system-( C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1iii.

Table 4iii: This table discloses 87 compounds T4iii.001 to T4iii.87 having the formula (Ic) wherein R is iC ₃ H ₇ , R ₁ , R ₂ , R ₃ and R ₄ are hydrogen, G-system-( C=O)CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1iii.

Table 5iii: This table discloses 87 compounds T5iii.001 to T5iii.87 having the formula (Ic) wherein R is hydrogen, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen, and G is - (C=O) CO-CH ₂ CH ₃ and R _a , R _b , R _c and R _d are as defined in Table 1iii.

Compounds of formula (I), including formulas (Ia), (Ib) and (Ic)), as well as processes for their preparation, formulations and adjuvants, are known from WO 2009/049851, WO 2010/063670 and WO 10/066780 .

Any one of the above compounds of T1.001 to T44.107, T1ii.001 to T38ii.107, and T1iii. to T8iii.87 may be selected as component A to be mixed with component B selected from at least one of the following: : a) pyridazine; b). Pyrethroids selected from the group consisting of: cyhalothrin, lambda-cyhalothrin, gamma-trichloro Cyfluthrin; c). A macrolide selected from the group consisting of abamidine, Emma Phytocin and ethyl spinosyn; d). Dioxamine selected from the group consisting of chlorantranyl benzylamine (Rynaxypyr®) and cyanzypyr® (Cyazypyr®); e) thiamethoxam; f) fluramide nitrile; g) oxazolidine; the invention includes all isomers of the compounds of formula (I), salts thereof and N-oxides, including enantiomers Constructs, diastereomers and tautomers. Component A can be a mixture of any type of isomers of the compound of formula (I), or can be substantially a single type of isomer.

Preferably, component B is selected from the group consisting of only one of the above a). to g). In other words, preferably, the present invention provides a two-component pesticidal mixture comprising component A of formula (I) (including formulas (Ia), (Ib), and (Ic) And a mixture of component B selected from one of a) to g). as an active ingredient.

Preferably, component B is selected from the group consisting of abamectin, cyanmethoxilam, emarosin, cyhalothrin, λ-three. Cyhalothrin, gamma-cyhalothrin, pyridazine, thiamethoxam, and chlorantraniliprole. More preferably, component B is selected from the group consisting of abamectin, cyanmethoxilam, chlorantraniliprole, emodin, lambda-three. Cyhalothrin, gamma-cyhalothrin, pyridazine, ethyl spinosyn, thiamethoxam, flonicamid, and oxazolidine.

In one embodiment, component B is selected from the group consisting of abamectin, cyanmethoxilam, emodin, lambda-cyhalothrin, Pyridazine, thiamethoxam, and chlorantraniliprole.

In another preferred embodiment, component B is selected from the group consisting of thiamethoxam, lambda-cyhalothrin, gamma-cyhalothrin, and Fluramide nitrile. The combination of a compound according to formula (I) for component A with at least one of these compounds for component B has the added advantage of a knock-down effect on a variety of pests, especially for powders虱 and locusts/plants. "Knockdown" means that the pest to be controlled is rapidly immobilized or killed completely (eg at least 80% mortality after 24 hours), thereby also reducing any disease associated with the spread of such pests. (eg virus) risk of infecting plants. Preferably, the active ingredient is a mixture of the above component A and a component B selected from at least one of the following, preferably only one, which is thiamethoxam, λ-trichlorofluoride Cypermethrin, gamma-cyhalothrin and flunicarbonitrile.

All components B from a) to g) are known, for example from the "The Pesticide Manual", fifteenth edition, edited by Clive Tomlin, British Crop Protection Council. )in.

References to component B above include references to salts thereof and any common derivatives, such as ester derivatives, and isomers.

Surprisingly, it has been found that the active ingredient mixture according to the invention not only brings about an additional reinforcement of the range of action of the pest to be controlled, but also achieves a synergistic effect of expanding the range of action of component A and component B in two ways. effect. First, the application ratio of component A and component B was lowered while the effect was also kept good. Second, the active ingredient mixture can still achieve a high degree of pest control, sometimes even where the two individual components have become completely ineffective over such low application rates. This allows for increased security in use.

However, in addition to the actual synergy of pest control, the pest killing according to the present invention The composition may have additional advantageous properties, such as synergistic activity, which may also be further illustrated in a broader sense. Examples of such advantageous properties which may be mentioned are: for other pests, such as resistant strains, an expansion of the range of pest control; a reduction in the ratio of active ingredient application; a sufficient pest with the aid of the composition according to the invention Control, even at the rate of application of individual compounds; advantageous behavior during formulation and/or application (eg, during milling, screening, emulsifying, dissolving or dispersing); increased storage stability; improved stability to light More favorable degradability; improved toxicological and/or ecotoxicological behavior; improved characteristics of useful plants including: germination, crop yield, more developed roots, increased tillering, increased plant height Larger leaves, fewer dead basal leaves, stronger tillers, greener leaf colors, less fertilizer needed, fewer seeds needed, more tillers, earlier flowering, Early maturity, fewer plants falling (falling), increased bud growth, improved plant vigor, and early germination; or any other familiarity familiar with the technique point.

The composition according to the invention may also comprise more than one active ingredient B if, for example, it is desired to expand the pest control range. For example, it may be advantageous to combine two or three component B with any of the compounds of formula (I) or with any of the compounds of formula (I) in an agricultural practice. In addition to components A and B, the mixtures of the invention may also include other active ingredients.

In other preferred embodiments, the active ingredient is a mixture of only component A and a single active component of component B as in list a). to g). In other words, the pesticidal composition preferably has no more than two pesticidal active components.

Each substituent definition in each preferred group of compounds of formula (I) may be juxtaposed in any combination with any substituent definition in any other preferred group of compounds.

The weight ratio of A and B is generally between 1000:1 and 1:100, more preferably between 500:1 and 1:100. In other embodiments, the weight ratio of A and B may be between 250:1 and 1:66, such as between 125:1 and 1:33, such as between 100:1 and 1:25, for example in Between 66:1 and 1:10, for example between 33:1 and 1:5, and so on. Such weight ratios result in a synergistic mixture.

The present invention also provides a pesticidal mixture which, as mentioned above, comprises a synergistically effective amount of a combination of components A and B together with an agriculturally acceptable carrier and optionally a surfactant.

The following mixtures are especially suitable for the treatment of peach aphid (green peach aphid):

The following mixtures are particularly suitable for the treatment of the two-spotted spider mites (two-spotted spider mites):

The invention also relates to a method of controlling insects, mites, nematodes or molluscs, comprising applying a combination of components A and B to pests, pests, or plants susceptible to pest attack; a seed of a mixture of B; a method comprising mixing a component A and B The compound is coated with seeds.

The amounts that components A and B can be provided and/or used are such that they are capable of synergistic pest control. For example, the invention includes a pesticidal mixture comprising a synergistically effective amount of component A and component B; an agricultural composition comprising a synergistically effective amount of a mixture of components A and B; synergistically effective amounts of components A and B The use of a mixture against animal pests; methods of combating animal pests, including the growth of animal pests, their habitat, breeding grounds, food supplies, plants, seeds, soil, areas, materials or pests therein a growing environment, or a material, plant, seed, soil, surface or space to be protected from attack or infestation by an animal, in contact with a synergistically effective amount of a mixture of components A and B; for protecting crops from animal harm A method of biological attack or infestation comprising contacting a crop with a synergistically effective amount of a mixture of components A and B; a method for protecting a seed from soil insects and roots and shoots of the shooter from soil and leaves Including contacting the seed with a synergistically effective amount of a mixture of components A and B before and/or before germination; the seed comprising, for example, a synergistically effective amount of coating a mixture of components A and B; a method comprising coating a seed with a synergistically effective amount of a mixture of components A and B; a method of controlling insects, mites, nematodes or molluscs, including pests, pests Or a plant susceptible to attack by a pest, applying a synergistically effective amount of a combination of components A and B. The mixture of A and B will normally be administered in an amount effective to kill insects, acaricidal, nematicidal or molluscicidal. In use, components A and B can be administered simultaneously or separately.

The mixture of the present invention can be used to control insect pests such as Lepidoptera, Diptera, Hemiptera, Thysanoptera, Orthoptera, Reticoptera, Coleoptera, Odonata, Hymenoptera, and Isoptera And other invertebrate pests, such as infestation of cockroaches, nematodes and mollusc pests. Insects, mites, nematodes and mollusks are collectively referred to herein as pests. These can be used by The pests controlled by the compounds of the present invention include pests associated with the storage of agricultural products (the term includes crops of food and fiber products), horticulture and livestock, pets, forestry, and vegetable sources (eg, fruits, grains, and wood); Pests associated with damage to man-made structures and the spread of disease in humans and animals; and nuisance pests (such as flies). The mixtures of the invention are particularly effective against insects, mites and/or nematodes. More particularly, the mixtures are effective against nematodes.

According to the invention, "useful plants" which can be applied with a mixture according to the invention typically comprise the following plant species: vines; cereals (for example wheat, barley, rye or oats); beets (such as beets or beets); (such as pear fruit, stone fruit or small seedless fruits such as apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries or blackberries); such as legumes (such as broad beans, lentils, peas or soybeans); Plants (such as rapeseed, mustard, poppy, olive, sunflower, coconut, castor oil, cocoa or groundnut); melons (such as tender gourds, cucumbers or melons); fiber plants (such as cotton, flax, hemp or jute) ) citrus fruits (such as orange, lemon, grapefruit or orange); vegetables (such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, gourds or red peppers); carp (eg avocado, medlar) (Cinnamonium) or camphor); corn; tobacco; nuts; coffee; sugar cane; tea; vines; hops; durian; banana; natural rubber tree; turf or ornamental (such as Flowers, shrubs, broadleaf trees or evergreen plants such as conifers). This list does not represent any restrictions.

The term "useful plant" is understood to also include the tolerance of herbicides such as bromoxynil or various herbicide classes (eg, HPPD inhibitors, ACCase inhibitors, ALS inhibitors, such as fluorine) due to conventional breeding methods or genetic engineering. Sulfasulfuron, flusulfuron and triflusulfuron, EPSPS (5-enol-acetone oxime-shikimate-3-phosphate-synthase) inhibitor, GS (glutamate synthase) inhibitor) Useful plants. An example of a crop that is rendered tolerant to imidazolinones (e.g., imazamox) by conventional breeding methods (mutagenesis) is Clearfield® Summer Canola (Canola). Examples of crops that have been rendered tolerant to herbicide or herbicide classes due to genetic engineering methods include glyphosate and glufosinate resistant maize varieties under the RoundupReady®, Herculex I® and LibertyLink® brand names. It is commercially available.

The term "useful plant" is understood to also include useful plants which have been transformed by the use of recombinant DNA techniques to enable the synthesis of one or more selectively acting toxins, such as those known to be derived from toxin producing bacteria, especially spores. Bacteria of the genus Bacillus.

Toxins which can be expressed by such transgenic plants include, for example, insecticidal proteins, such as insecticidal proteins from Bacillus cereus or Bacillus cerevisiae; or insecticidal proteins from Bacillus thuringiensis, such as delta-endotoxin, For example, Cry1A (b), Cry1A (c), Cry1F, Cry1F (a2), Cry2A (b), Cry3A, Cry3B (b1) or Cry9c, or plant insecticidal protein (Vip), such as Vip1, Vip2, Vip3 or Vip3A Or colony forming nematode insecticidal proteins, such as the genus Bacillus or the genus Bacillus, such as luminescent bacillus, nematophagous pathogenic bacilli; animal-derived toxins such as scorpion toxin, spider toxin, melittin and others Insect-specific neurotoxins; toxins produced by fungi, such as streptomyces toxins, plant lectins such as pea lectin, barley lectin or snowdrop lectin; lectins; protease inhibitors such as trypsin inhibitors, silkamines Acid protease inhibitor, potato tuber specific protein (papatin), cysteine protease inhibitor, papain inhibitor; ribosome inactivating protein (RIP), such as ricin, corn-RIP, phase Bean toxic protein, loofah toxic protein, saporin toxin protein or diarrhea toxic protein; steroid metabolism enzymes such as 3-hydroxy steroid oxidase, steroid steroid-UDP-glycoside-transferase, cholesterol oxidase, suede Inhibitors, HMG-COA-reductase, ion channel blockers such as sodium or calcium channel blockers, child care Hormone esterase, diuretic hormone receptor, purine synthase, bibenzyl synthase, chitinase and glucanase.

In the context of the present invention, delta-endotoxins such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or plant-based insecticidal proteins (Vip), such as Vip1, Vip2, Vip3 or Vip3A, are understood to be apparently also These include mixed toxins, truncated toxins, and modified toxins. Mixed toxins are produced by recombination of new combinations of different regions of those proteins (see, for example, WO 02/15701). An example of a truncated toxin is the truncated Cry1A (b), which is expressed in Bt11 corn from Syngenta Seeds SAS (see Syngenta Seeds) as described below. In the case of a modified toxin, one or more amino acids of the naturally occurring toxin are replaced. In this amino acid substitution, it is preferred to insert a non-naturally occurring protease recognition sequence into the toxin, for example in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into the Cry3A toxin (see WO 03/018810). ).

Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.

Methods for preparing such transgenic plants are known to those skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

Toxins contained in transgenic plants make plants resistant to harmful insects. Such insects may be present in any insect taxonomic group, but are especially found in beetles (coleoptera), double-winged insects (Diptera), and butterflies (Lepidoptera).

Transgenic plant lines containing one or more genes encoding insecticide resistance and expression of one or more toxins are known and some of them are commercially available. An example of such a plant is: YieldGard® (Maize variety, expressing Cry1A (b) toxin); YieldGard Rootworm® (corn variety, expressing Cry3B (b1) toxin); YieldGard Plus® (corn variety, expressing Cry1A (b) and Cry3B (b1) toxin); Starlink® ( Maize varieties, expressing Cry9(c) toxins; Herculex I® (corn varieties, Cry1F(a2) toxins and phosphinothricin N-acetyltransferases that achieve tolerance to the herbicide glufosinate ( PAT)); NuCOTN 33B® (cotton variety, expressing Cry1A (c) toxin); Bollgard I® (cotton variety, expressing Cry1A (c) toxin); Bollgard II® (cotton variety, expressing Cry1A (c) and Cry2A (b) ) toxin); VipCOT® (cotton variety, expressing Vip3A and Cry1Ab toxin); NewLeaf® (potato variety, expressing Cry3A toxin); NatureGard® and Protecta®.

Other examples of such GM crops are:

1. Bt11 corn from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified maize, by transgenic expression of the truncated Cry1A(b) toxin, is resistant to attack by European corn borer (corn borer and pink stem borer). Bt11 maize also transgenicly expresses the PAT enzyme to achieve tolerance to the herbicide glufosinate ammonium salt.

2. Bt176 corn from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified maize, by transgenic expression of Cry1A(b) toxin, is resistant to attack by European corn borer (corn borer and pink stem borer). Bt176 maize also transgenicly expresses the PAT enzyme to achieve tolerance to the herbicide glufosinate ammonium salt.

3. MIR604 corn from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. The insect-resistant corn is made by transgenic expression of a modified Cry3A toxin. This toxin is made by inserting tissue eggs Cry3A055 modified by the white enzyme-G-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.

4. MON 863 Corn , from Monsanto Europe SA, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses Cry3B (b1) toxin and is resistant to certain coleopteran insects.

5. IPC 531 cotton from Monsanto 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/ES/96/02.

6. 1507 Corn , from Pioneer Overseas Corporation Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize, expressing the protein Cry1F to achieve resistance to certain lepidopteran insects and expressing PAT protein to achieve tolerance to the herbicide glufosinate ammonium salt.

7. NK603×MON 810 corn from Monsanto, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. By hybridizing the genetically modified variety NK603 and MON810, it is composed of a conventionally cultivated hybrid corn variety. NK603×MON 810 maize transgenic expression of the CP4 EPSPS protein obtained from Agrobacterium strain CP4, which confers the herbicide tolerant Roundup® (containing glyphosate), as well as from the Bacillus thuringiensis Kustaque subspecies Obtained CryIA(b) toxin which renders the corn resistant to certain lepidopteran insects, including European corn borer.

Transgenic crops of insect-resistant plants are also described in BATS (Basel 4058, Switzerland, Clarastrasse 13, Zentrum für Biosicherheit und Nachhaltigkeit, Zentrum BATS) Report 2003 (http://bats.ch) ).

The term "useful plant" is understood to also include having been transformed by the use of recombinant DNA technology. A useful plant capable of synthesizing a selective anti-pathogenic substance, such as, for example, a so-called "pathogenesis-related protein" (PRP, see for example EP-A-0 392 225). Some examples of such anti-pathogenic substances and transgenic plants capable of synthesizing such anti-pathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818 and EP-A-0 353 191. Such methods of producing such transgenic plants are generally known to those skilled in the art and are described, for example, in the above publications.

Anti-pathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers such as sodium and calcium channel blockers, such as viral KP1, KP4 or KP6 toxins; purine synthase, bibenzyl synthesis Enzyme; chitinase; glucanase; so-called "pathogenesis-associated protein" (PRP, see for example EP-A-0 392 225); anti-pathogenic substances produced by microorganisms, such as plant pathogen defense Peptide antibiotics or heterocyclic antibiotics (see for example WO 95/33818) or protein or polypeptide factors (so called "plant disease resistance genes", as described in WO 03/000906).

Useful plants of more interest in connection with the present invention are cereals; soybeans; rice; canola; pear fruit; stone fruit; peanuts; coffee; tea; strawberries; turf; vines and vegetables such as tomatoes, potatoes, gourds and lettuce.

As used herein, the term "place" of a useful plant is intended to encompass the place where the plant is grown, where the plant propagation material of the useful plant is sown, or where the propagation material of the useful plant will be placed in the soil. An example of such a site is a field on which crop plants are grown.

The term "plant propagation material" is understood to mean the reproductive part of a plant, such as seeds, which parts can be used for the propagation of the latter, as well as plant-based materials such as cuttings or tubers (for example potatoes). Mention may be made, for example, of seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. It can also be mentioned that after germination or after germination from the soil Germinated plants and young plants. These young plants can be protected prior to transplantation by impregnation in whole or in part. Preferably, "plant propagation material" is understood to mean a seed. Particularly interesting insecticides for treating seeds include thiamethoxam, indoleamine and clothianidin.

A further aspect of the invention is a method of protecting a natural substance and/or a processed form thereof derived from a plant and/or animal source of the natural life cycle from pests, comprising combining a synergistically effective amount of component A and B A natural substance or a processed form thereof that is applied to the plant and/or animal source.

According to the invention, the term "natural material derived from a plant source of the natural life cycle" means a plant or part thereof harvested from the natural life cycle and in freshly harvested form. Examples of such plant-derived natural substances are stems, leaves, tubers, seeds, fruits or grains. According to the invention, the term "processed form of a natural substance of plant origin" is understood to mean the form of a natural substance of the plant source as a result of the modification process. Such a modification process can be used to convert a plant-derived natural substance into a form in which such a substance is more suitable for storage (storage of goods). Examples of such modification processing are pre-drying, wetting, crushing, pulverizing, grinding, compressing or calcining. Also defined by the processing form of the natural material of the plant source is wood, whether in the form of logs, such as construction timber, transmission towers and fences, or in the form of finished goods, such as furniture or objects made from wood.

According to the invention, the term "natural material derived from an animal source of the natural life cycle and/or its processed form" is understood to mean an animal-derived material such as hide, hide, leather, fur, hair and the like.

A preferred embodiment is a method of protecting a natural source of a plant source derived from a natural life cycle and/or a processed form thereof from attack by a pest, comprising applying a synergistically effective amount of a combination of components A and B to said A natural substance of plant and/or animal origin or a processed form thereof.

Another preferred embodiment is a method of protecting fruits (preferably pear, stone, non-nuclear and citrus fruits) and/or their processed forms taken from the natural life cycle, which comprises synergistically effective amounts of The combination of components A and B is applied to the fruit and/or their processed form.

The combination according to the invention is further particularly effective against the following pests: aphid (aphid), cotton aphid (aphid), black soybean meal (aphid), grasshopper, (blind), cotton red genus, (blind ), rice brown planthopper (flying planthopper), black-tailed leafhopper (leaf leafhopper), green genus (skunk), American genus (skunk), rice genus (skunk), western flower hummer ( Hummer), Hummer (Puma), potato beetle (potato beetle), Mexican boll weevil (cotton bell weevil), kidney genus genus (scale insect), whitefly (whitefly), whitefly ( Whitefly, European corn borer (European corn borer), Spodoptera frugiperda (cotton leaf worm), H. californica (Sphingidae), Helicoverpa armigera (H. armigera), H. californica (Hübner) Cotton leafhopper (Cotton leafhopper), large cabbage butterfly (Pink butterfly), Plutella xylostella (Plutella xylostella), Diptera (G. chinensis), Chilo suppressalis (Strontium chinensis), Aphis gossypii (Aphididae), Australian plague Aphids (Aphids), Radix Aurantia (rootworm), Apple Whole Claw (Apple Red Spider), Orange Whole Claw (Citrus Red Spider), Two-spotted Leafhopper (Two-spotted Leafhopper), Vermilion Leafhopper ( Red spider), orange rust rust (citrus rust 螨), side multi-food 跗 line 螨 (tea螨), Short-striped genus (Grass squid), tiny burdock (with ring burdock), variegated scorpion (American cockroach cockroach), cat cockroach cockroach (cat cockroach), genus Liriomyza (Lepidoptera) ), housefly (housefly), Aedes aegypti (mosquito), Anopheles (mosquito), Culex (mosquito), Greenfly (Bloodfly), German cockroach (蟑螂), American cockroach (蟑螂), Oriental cockroach (蟑螂), termites of the Australian termite family (such as the Australian termite genus), wood termites (such as the new termite genus), rhinoceros family (such as Taiwanese termites, flavonoids, yellow-breasted termites, Southern termites, western termites and Sant's termites, and termites (eg, Globitermes sulfurus), tropical fire ants (fire ants), small yellow ants (Pharaoh ants), genus and ranunculus (biting and sucking), root-knot nematode (root knot nematode), Helminthosporium and Heterodera (cyst nematode), genus Nematode (Helicidae), Pleurotus (Banana sinensis), Nematodes (Citrus elegans), Haemonchus contortus (捻 胃 worm), Caenorhabditis elegans (V. elegans), Trichophyton genus (gastrointestinal nematode) and reticulated wild cricket (蛞蝓).

In another embodiment, the combination according to the invention is also particularly effective against the following pests: from the order of the genus, for example, the genus Hymenoptera, the genus Robinia , Acaricalus spp., the genus Tumor, the genus Cyclops , genus, burdock , genus, genus, genus, genus, genus (C alipitrimerus spp.), genus, pheasant, echinoderma , genus Genus, genus, genus, genus, genus, genus, genus, genus, genus, genus, genus, genus, genus, Phytonmus spp , 跗, 螨, 螨, 扇, 根, 疥螨, 疥螨, 斯, 跗, 螨, and genus; from the eye, for example, blood Genus, genus, genus, pemphigus and hibiscus; from Coleoptera, for example, genus Amphimallon , Amphimallon majale , Oriental genus, genus, genus, Astylus atromaculatus, Ataenius spp, Atomaria linearis, beet mites, Cerotoma spp, genus, genus, green turtle , genus, genus, genus, genus, genus, genus Diloboderus abderus , genus Eremus , Eremnus spp., black- spotted cane, tortoise, Lagria vilosa , Potato beetle, Lysimachia , Liogenys spp, Maecolaspis spp, Marsh velvet golden tortoise, Megascelis spp, Melighetes aeneus , Cervigo , Myochrous armatus , Sawgrass , Otiorhynchus spp., Cerambycidae , Species, genus, genus, Rhyssomatus aubtilis , genus, genus, genus, genus, genus Pseudomonas , Sphenophorus spp, stalks, genus From the order of the Diptera, for example, Aedes, Anopheles, Sorghum, Bactrocea oleae , Garden Mosquito, Hymenoptera, Red-headed Fly, Strip fly Genus, genus, genus, genus, genus, genus, genus, genus, genus, genus, genus, genus Geomyza tripunctata , genus, genus, genus Musca, Liriomyza, Green Fly, Black Dive Spp., Musca spp, mad fly genus, gall midge species, Sweden straw flies, quinoa spring flies, fly genus grass, around the fruit fly genus, Rivelia quadrifasciata, Scatella spp., Mushroom mosquito species, genus barbed flies, Tabanus , genus Aphid and the genus Heliconia ; from the Hemiptera, for example, Acanthocoris scabrator , Eucalyptus, 苜蓿 蝽 , Amblypelta nitida , Bathycoelia thalassina , genus, Bacillus , Clavigralla tomentosicollis , 淡蝽 , 哥哥 Diemonops , Dichelops furcatus , H. sinensis , Edessa spp, E. sinensis, Eurydema pulchrum , Eurygaster spp., Diptera , Horcias nobilellus , Osmanthus chinensis , grass Phyllostachys, genus, genus Murgantia histrionic , Neomegalotomus spp, scorpion scorpion , Nezara spp., Nysius simulans , Oebalus insularis, scutellaria, Piezodorus spp, red scorpion genus 蝽 , Scaptocoris castanea , Scotinophara spp., Thyanta spp, Cone genus, Vatiga illudens Acyrthosium pisum , Adalges spp, Agalliana ensige ra, Agonoscena targionii, Chinese pistache, whiteflies belong (Aleurodicus spp.), spiny whitefly, Saccharum points whitefly, fur whitefly, vegetables whitefly, Amarasca biguttula, Amritodus atkinsoni, kidney Kuwana is a buckler, aphids蚜, 蚧, 茄, 茄, B, Bactericera cockerelli , 虱 , 舌, 甘, 甘 , 喀 , 二, 蚧, 黑, 黑Chrysomphalus aonidium ), net stalk , scutellaria , genus, leucocysae , genus, genus, genus, genus, genus, genus, citrus, citrus , Western genus, genus, genus, cotton aphid, genus, genus, genus, genus, genus Hydra genus, Hyadaphis pseudobrassicae , Eucalyptus, Hyperomyzus palludus , mango green leaf, Jacobiasca lybica, planthopper genus Didesmococcus, oyster shield Kuwana genus, Lopaphis erysimi, Lyogenys maidis, aphid genus (Macrosiphum spp.), Mahanarva spp , Metcalfa pruinosa, wheat aphid, wheat planthoppers, aphids is a tumor , Neotoxoptera sp, black Eucalyptus, brown plant , Ophiopogon japonicus , Odonaspis ruthae , sugarcane cotton aphid, red bayberry, Paratrio cockerelli , scutellaria, scorpion , corn wax, flat Perkinsiella spp, 疣蚜布疣蚜, 根属, 臀, 白, 蚧, 蚧, 蝽, 蝽, 虱, 蚧, 蚧 , Quesada gigas , electro-optic leafhopper, genus genus, genus, genus, genus, genus, genus Sitobion spp., white-backed locust , Spissistilus festinus , striata Toxoptera spp, Trialeurodes spp, Tridiscus sporoboli , Amaranthus , African hibiscus , Zangina flammigera , Zygihidia scutellaris , from Hymenoptera, for example, top cut Genus, Arge spp, Arbor , genus, genus, genus, genus Gilpinia polytoma , genus Papilio, genus small yellow house ant, new pine sawfly genus, the genus to be leaf-cutting ants, Slenopsis invicta, water ant genera and Hu Genus; from the Isoptera, for example, is a termite, Corniternes cumulans, Ying belongs to termites, termites belong, Australia termites is a small genus of termites, termite genera; tropical fire ants from the Lepidoptera, for example, long-winged moth genus , genus, genus, genus, genus, cotton leaf worm, Amylois spp., larvae, genus, genus Argyresthia spp, genus Noctuidae, cotton moth, corn borer moth, pink spotted moth, peach aphid, grass genus, leaf genus, Chrysoteuchia topiaria, grape fruit moth, leaf genus, genus , Moth, Moth, Moth, Physalis, Cosmophila flava, Crambus spp, Cauliflower, Apple, Moth, Cydalima perspectalis, Moth, Populus euphratica Diaphania perspectalis, genus Salicornia, Helicoverpa armigera, Earias spp., Eldana Saccharina, Ephestia kuehniella, Pinus massoniana (Epinotia spp) .), Estigmene acrea fine spotted moth, soy bean pod Etiella zinckenella, flower small moth Genus, ring-shaped single moth, yellow toad, genus, genus Feltia jaculiferia, genus, genus Hedya nubiferana, genus Helicover, genus, black-spotted cane tortoise (Heteronychus arator ), American white moth, Keiferia lycopersicella, Lasmopalpus lignosellus, Cymbidium moth, Lepidoptera, Loxostege bifidalis, Lymantria spp., Lithophyllum , Curcuma, Cabbage, Moth, Toxoplasma, Mythimna spp, Noctua spp, Aphididae, Orniodes indica, European corn borer, Ultramania, Brown-eyed moth, small eye Noctuid, cotton bollworm, potato moth, coffee leaf miner, armyworm (Pseudaletia unipuncta), potato tuber moth (Phthorimaea operculella), cabbage butterfly, Pieris, Plutella xylostella, Spodoptera, Spodoptera Spp), Rachiplusia nu, Richia albicosta, genus, genus, genus, genus, genus, genus Sylepta derogate, genus, genus Genus, Coleus, Spodoptera Phytophthora sojae (Tuta absoluta) and the genus Corydalis; from the genus Corydalis, for example, the genus Damalina spp. and the genus Echinochloa; from the Orthoptera, for example, the genus Amaranthus, the genus Euphorbia, the genus Madeira, scorpion, northern scorpion, Euphorbia, genus, and desert genus; from the order of the genus, for example, the genus of the genus; from the genus, for example, the genus Genus and Kaihuang Hakka; from the order of the genus Hymenoptera, for example, Calliothrips phaseoli , Phyllostachys pubescens , Pseudostellaria , Trichosanthes , Parthenothrios spp, South African citrus thrips, soybean thrips, Pteropus , 蓟 genus; from the appendix, for example, the fish.

The active ingredients according to the invention can be used for control, ie limitation or destruction, on plants, especially on plants, especially in useful plants and ornamental plants in agriculture, horticulture and forests, or in organs of such plants If the above-mentioned types of pests on the leaves, flowers, leaves, stalks, tubers or roots, and in some cases even on plant organs formed at later time points, protection against such pests.

The mixtures of the present invention can be used to control pests of a variety of plants, including soybeans, alfalfa, alfalfa, or oil crops such as canola, mustard, canola, poppy, olive, Sunflower, coconut, ramie, cocoa or groundnut, or potato (including sweet potato), almonds, fruit vegetables (such as tomatoes, peppers, red peppers, eggplant, cucumber, pumpkin, etc.), bulbous vegetables (such as onions, alfalfa, etc.) ), grapes, fruits, such as pome fruit, stone fruit and small non-nuclear fruits (such as apples, pears, plums, peaches, almonds, cherries, etc.) or berries, such as strawberries, cranberries or blackberries.

Other suitable target crops are especially cereals such as wheat, barley, rye, oats, rice, corn or sorghum; beets such as sugar or fodder beet; legumes such as beans, lentils, peas, or soybeans; Cucurbitaceae, such as pumpkin, cucumber or melon; fiber plants such as cotton, flax, hemp or jute; citrus fruits such as citrus, lemon, grape sleeves or red orange; vegetables such as spinach, lettuce, asparagus, cabbage Carrots, onions or sweet peppers; medlars such as avocados, eucalyptus or camphor; and tobacco, nuts, coffee, eggplant, sugar cane, tea, pepper, grapes, hops, plantain, latex plants and ornamental plants.

The mixture of the present invention can be used for controlling soybeans, for example, South American corn seedlings, Argentine worms, South American stalks, soybean stalks, formicidae , snails , Julus sspp. , Lithoga genus, Megascelis ssp. , Andus potato genus, Polygonaceae, Southern green pheasant, genus, genus, Neomegalotomus spp. , Beans , Japanese chafer , Edessa spp. , Liogenys fuscus, Euchissus heros , Common stalk, Moth, Scaptocoris Castanea , horned genus, soybean, and genus Heliothis, B. tabaci, and genus. The mixture of the present invention is preferably used for controlling argentinian argus, southern American genus, southern green pheasant, genus, genus, genus, lentil , Japanese chafer , Euchistus heros , genus, and genus The genus is a genus.

The mixtures of the present invention can be used in corn control, for example, Euchistus heros , Dichelops furcatus , Argentine worms, South American corn seedlings, Grasshopper moth, Southern green pheasant, Bean Bean, Japanese chafer, small land Tiger, South American leaf, Heteroptera, Andus genus, Scaptocoris castanea , Formicidae, Julus ssp. , Corn yellow leafhopper, Corn genus, South American locust , Bemisia, Heliothis , Astragalus , Thrips, A. scaptocoris spp., Liogenys fuscus , Heliothisus, Corn genus, Spodoptera, and genus. The mixture of the present invention is preferably used for controlling the Euchustus heroes , Dichelops furcatus, Argentine chinensis , Southern green pheasant , Dioscorea opposita , Japanese chafer, South American leaf beetle, Corn genus, Aphis, Aphis Equus, horned genus, scaptocoris spp. , genus.

The mixture of the invention can be used in sugar cane to control, for example, the genus, the termite, Mahanarva spp . The mixture of the invention is preferably used in sugar cane to control termites, Mahanarva spp.

The mixture of the present invention can be used for controlling cockroaches , for example, worm weevil, sable leaf, scutellaria , Collops spp. , Empoasca solana , scorpion genus, big eye scorpion Genus, pea pods, American grasshoppers, genus Hymenoptera, Spodoptera, and Spodoptera litura. The mixture of the present invention is preferably used for controlling worms, larvae, sylvestris, Solana, genus, genus, genus, genus, and larvae.

The mixture of the present invention can be used for controlling cockroaches, for example, the diamondback moth, the genus Cabbage, the genus Brassica, the genus Heliothis, the genus Spodoptera, the genus, the genus Spodoptera, and the genus A small green leafhopper, a genus of the genus, a genus of the genus Heliothis, and a genus of the genus. The mixture of the present invention is preferably used for controlling peony, Plutella, Heliothis, Spodoptera, Spider, and Thrips.

The mixture of the present invention can be used in canola (e.g., Canola) to control, for example, the genus Asparagus, the weevil, and the genus Brassica.

The mixture of the present invention can be used for potato (including sweet potato) to control, for example, the genus Corydalis, the genus Bacillus, the genus Prunus, the genus Solanum, the Paratrioza spp., the terrapin, and the genus. The mixture of the present invention is preferably used in potato including sweet potato to control the genus Helianthus, the genus Bacillus, the genus Pteroma, the genus Solanum, the Paratrioza spp. , and the genus.

The mixture of the present invention can be used for cotton control, for example, Mexican cotton boll, red bollworm, Heliothis, Heliothis, Aphis, Euonymus, Thrips, B. tabaci, Grasshopper, genus, and Scaptocoris spp . The mixture of the present invention is preferably used in cotton to control Mexican cotton bolls, spider mites, small green leaf genus, genus genus, genus genus, genus, and Scaptocoris spp .

The mixture of the present invention can be used for controlling rice, for example, rice genus, genus, genus, genus, genus, genus, and rice blast. The mixture of the present invention is preferably used in rice to control rice genus, rice genus, and American rice blast.

The mixture of the present invention can be used for coffee control, for example, coffee berry, coffee leaf miner, spider mites. The mixture of the present invention is preferably used in coffee to control coffee berry, coffee leaf miner.

The mixture of the present invention can be used for controlling citrus, for example, T. citrifolia, T. urticae, Berberis, Citrus hibiscus, Hard genus, Thrips, genus, genus , leaf genus. The mixture of the present invention is preferably used in citrus to control the orange scorpion, the citrus rust, the genus citrus, the citrus eucalyptus, the hard hummer, the genus, and the genus.

The mixture of the present invention is used for controlling almonds, for example, umbelliferae, spider mites.

The mixture of the invention can be used for fruit vegetables including tomatoes, peppers, peppers, eggplants, cucumbers, pumpkins, etc. to control the genus of the genus Thrips, the genus Aphis, the genus Polygonum, the genus Phyllostachys, the genus , Spodoptera, Spodoptera, Liriomyza sativae, Liriomyza, B. tabaci, Amaranthus , Paratrioza spp. , Western flower thrips, flower thrips, flower genus, strip jump A, genus, genus, genus Halyomorpha spp. , hard hummer , genus, genus Neoleucinodes spp . The mixture of the present invention is preferably used for fruit vegetables including tomatoes, peppers, peppers, eggplants, cucumbers, squash, etc. to control, for example, genus Thrips, spider mites, Polyphagotarsonemus spp. , thorns, small green leaves Genus, Spodoptera, Spodoptera, Liriomyza sativae, Liriomyza spp. , Paratrioza spp. , Western flower thrips, flower thrips, Rhododendron, hard thrips, white-winged Wild genus, Neoleucinodes spp .

The mixture of the present invention can be used for tea control, for example, the genus White Shield, the small green leaf genus, the hard humus, and the tea moth. The mixture of the present invention is preferably used in tea to control the small green leaf genus, the hard genus.

The mixture of the present invention can be used for bulbous vegetables (including onions, alfalfa, etc.) to control, for example, Thrips, Spodoptera, Spodoptera. The mixture of the present invention is preferably used for bulbous vegetables (including onions, alfalfa, etc.) to control, for example, the genus Thrips.

The mixtures of the invention may be used in the control of grapes, for example, the small green leaf genus, the genus Hymenoptera, the genus Thrips, the genus Thrips, the genus Amaranthus, the damselfly , the Eotetranychus Willamettei , the grape bud , Scaphoides spp. The mixture of the present invention is preferably used for controlling grape genus, genus, genus, genus, scorpion, Scaphoides spp .

The mixture of the present invention can be used for control of pear fruit (including apples, pears, etc.), for example, eucalyptus, hibiscus, apple scorpion, and codling moth. The mixture of the present invention is preferably used for pear fruit (including apples, pears, etc.) to control the genus Kasuga, hibiscus, and apple scorpion.

The mixture of the present invention can be used for stone fruit to control, for example, P. grisea, E. striata, Thrips, Thrips, and Aphis. The mixture of the invention is preferably used for stone fruit to control hard Thrips, genus, genus, genus.

The amount of the combination of the invention to be applied will depend on various factors such as the compound used; the target of the treatment (such as, for example, plants, soil or seeds); the treatment form (such as, for example, spraying, dusting or seed dressing); (such as, for example, prevention or treatment); the type of pest to be controlled or the time of administration.

Mixtures comprising a compound of formula (I), for example those selected from the above tables, and one or more active ingredients as described above may be applied, for example, in the form of a single "water ready to use", in combination with a spray mixture (the mixture consists of a separate formulation of the single active ingredients) (eg, a "tank mix"), and when in a sequential manner (ie, one after another suitable short period of time, such as hours or days) Applying the individual active ingredients in combination at the time of administration. The application of, for example, a compound of formula (I) selected from the above tables and the above-described active ingredients is not critical to the practice of the invention.

The synergistic activity of the combination is evident from the fact that the pesticidal activity of the composition of A+B is greater than the sum of the pesticidal activity of A and B.

The method of the invention comprises applying the synergistically effective total of component A and component B as a blend or separately to a useful plant, its locus or its propagation material.

Some of the combinations according to the invention have a systemic action and can be used as a pesticidal agent for on-leaf, soil and seed treatment. The invention also encompasses a method comprising coating a seed with a mixture of component A and component B as defined above.

Using the combination according to the invention, it is possible to inhibit or destroy pests which occur on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of a plurality of different useful plants, while also protecting Part of the plant that grows later is protected from attack by pests.

Combinations of the invention are useful for controlling pests in different useful plants or their seeds Not meaningful, especially in field crops such as potatoes, tobacco and beets as well as wheat, rye, barley, oats, rice, corn, lawn, cotton, soybeans, canola, pod crops, sunflowers, coffee, sugar cane, in gardening And the fruit of the grape growing and the ornamental plants, in vegetables (such as cucumbers, beans and gourds).

A combination according to the invention is a useful plant, a site thereof, a propagation material thereof, a plant taken from the natural life cycle, and/or a plant that is threatened by a combination of components A and B in a synergistically effective amount, in the presence of a pest. Or animal derived natural material and/or its processed form, or industrial material.

The combination according to the invention may be applied before or after the useful plant, its propagation material, the natural material of the plant and/or animal source derived from the natural life cycle and/or its processed form, or the industrial material is infested or contaminated by the pest. .

Combinations according to the invention and can be used to control, ie limit or destroy, the presence of useful plants in agriculture, horticulture and forests, or in the above-mentioned types of organs, leaves, stems, tubers or roots of useful plants The pests, and in some cases, maintain protection against such pests even on useful plant organs formed at later time points.

When applied to a useful plant, the compound having the formula (I) is generally applied in a ratio of from 1 to 500 g ai/ha of a component B in combination with from 1 to 2000 g ai/ha, depending on the chemistry used as component B. Product category.

Generally for plant propagation materials (such as seed treatment), the application rate can range from 0.001 g active ingredient per kg seed to 10 g active ingredient per kg seed. When the combination of the invention is used to treat seeds, from 0.001 g to 5 g of compound of formula (I) per kg of seed (preferably 0.01 g to 1 g per kg of seed) and 0.001 g per kg of seed 5 g of component B compound (compared Preferably, a rate of from 0.01 g to 1 g per kg of seed is usually sufficient.

The genus Noctuidae preferably refers to the genus Spodoptera. The genus Spodoptera preferably refers to the budworm. Preferably, spider mites are two-spotted spider mites.

The composition of the present invention can be used in any conventional form, for example, a powder (DS) for double-packaging, dry seed treatment, an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), Solution for seed treatment (LS), water-dispersible powder for seed treatment (WS), capsule suspension for seed treatment (CF), gel for seed treatment (GF), emulsion concentrate (EC), suspension Concentrate (SC), Suspension Emulsion (SE), Capsule Suspension (CS), Water Dispersible Granule (WG), Emulsifying Granule (EG), Water-in-Board Emulsion (EO), Oil-in-water Type Emulsion (EW), microemulsion (ME), oil dispersant (OD), flowable miscible oil (OF), oil miscible liquid (OL), soluble concentrate (SL), ultra low volume suspension (SU), ultra low volume liquid (UL), industrial concentrate (TK), dispersible concentrate (DC), wettable powder (WP), soluble granule (SG) or agriculturally acceptable Any technically feasible formulation form of the combination of adjuvants.

Such compositions can be prepared in a conventional manner, for example, by mixing the active ingredient with a suitable formulation of inerts ( diluents, solvents, fillers, and optionally other ingredients, such as surfactants, biocides, antifreeze, adhesives) Agents, thickeners and compounds that provide adjuvant effects). Conventional sustained release formulations intended to achieve long lasting efficacy can also be used. Formulations which are especially applied in the form of a spray, such as a water-dispersible concentrate (for example EC, SC, DC, OD, SE, EW, EO and the like), a wettable powder and granules, may comprise a surfactant such as a moisturizer And dispersing agents and other compounds which provide adjuvant effects, such as formaldehyde and naphthalene sulfonate, alkylaryl sulfonates, lignosulfonates, fatty alkyl sulfates and ethoxylated alkylphenols and ethoxylates A condensation product of a fatty alcohol.

The compositions according to the invention may preferably additionally comprise additives comprising oils of vegetable or animal origin, mineral oils, alkyl esters of such oils or mixtures of such oils with oil derivatives. The amount of oil additive used in the composition according to the invention is generally from 0.01% to 10% of the spray mixture. For example, the oil additive can be added to the spray can at a desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral oil or vegetable derived oils such as rapeseed oil (such as ADIGOR® and MERO®), olive oil or sunflower oil, emulsified vegetable oils such as AMIGO® (Rona-Planck Canada) (Rhône-Poulenc Canada Inc.), an alkyl ester of a vegetable derived oil, such as a methyl derivative, or an animal derived oil such as fish oil or tallow. Preferred additives comprise, for example, substantially 80% by weight of fish oil alkyl esters and 15% by weight of methylated rapeseed oil, and also 5% by weight of commonly used emulsifiers and pH modifications. The agent acts as an effective component. And especially oil additives comprise alkyl esters of C ₈ -C ₂₂ fatty acids, especially the methyl derivatives of C ₁₂ -C ₁₈ fatty acids, for example, important lauric acid, palmitic acid and oleic acid, methyl ester. Those esters are known as methyl laurate (CAS-111-82-0), methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112-62-9). Preferred fatty acid methyl ester derivatives are Emery® 2230 and 2231 (Cognis GmbH). Those and other oil derivatives are also known in the "Compendium of Herbicide Adjuvants" (2000, Southern Illinois University, 5th Edition). Also, alkoxylated fatty acids can be used as additives in the compositions of the invention, and as polymethyl siloxane based additives, as described in WO 08/037373.

The use and effect of such oil additives can be further improved by combining them with surface active materials such as nonionic, anionic or cationic surfactants. Examples of suitable nonionic, anionic or cationic surfactants are listed on pages 7 and 8 of WO 97/34485. Preferred surface active materials are anionic surfactants of the dodecanebenzyl sulfonate type, especially the calcium salts thereof, and also nonionic surfactants of the fatty alcohol ethoxylate type. Particularly preferred is given degree of ethoxylation of C 5 to 40. ₁₂ -C ₂₂ fatty alcohols. An example of a commercially available surfactant is the Genapol type (Clariant AG). Also preferred are polyoxyxides, especially polyalkyl-oxide-modified heptamethyltrioxane, which are commercially available, for example, as Silwet L-77®, and perfluorinated. Surfactant. The concentration of the surface active substance associated with such an overall additive is generally from 1% to 30% by weight. Examples of oil additives consisting of a mixture of oils or mineral oils or their derivatives and surfactants are Edenor ME SU®, Turbocharge® (Syngenta AG, CH) and Actipron® (BP oil). BP Oil UK Limited (GB)).

The surface active substances can also be used alone in the formulation, that is to say without the use of oil additives.

Furthermore, the addition of an organic solvent to the oil additive/surfactant mixture can contribute to further enhancement. Suitable solvent systems are, for example, Solvesso® (ESSO) and Aromatic Solvent® (Exxon Corporation). The concentration of such a solvent may be from 10% to 80% by weight based on the total weight. Such oil additives can be mixed with a solvent and are described, for example, in US-A-4 834 908. The commercially available oil additive disclosed therein is named MERGE® (BASF). Another preferred oil additive in accordance with the present invention is SCORE® (Syngent Canada).

In addition to the oil additives listed above, in order to enhance the activity of the compositions according to the invention, it is also possible to add a formulation of an alkylpyrrolidone (for example Agrimax®) to the spray mixture. Formulations of synthetic latexes such as, for example, polyacrylamide, polyvinyl compounds or poly-1-p-menthene (e.g., Bond®, Courier® or Emerald®) can also be used. A solution containing propionic acid, such as Eurogkem Pen-e-trate®, can also be mixed into the spray mixture. An agent that enhances activity.

The seed dressing formulations are applied to the seed in a manner known per se using the combinations and diluents of the invention in the form of a suitable seed dressing formulation, for example in the form of an aqueous suspension or dry powder having good adhesion to the seed. Such seed dressing formulations are known in the art. Such seed dressing formulations may comprise a single active ingredient or a combination of active ingredients in encapsulated form, such as a sustained release capsule or microcapsule. Typical tank mix formulations for seed treatment applications include from 0.25% to 80%, especially from 1% to 75%, of the desired ingredients, and from 99.75% to 20%, especially from 99% to 25% solids or liquids. Agents (including, for example, solvents such as water), wherein the adjuvants may be surfactants in an amount of from 0 to 40%, especially from 0.5% to 30%, based on the tank mix. Typical premix formulations for seed treatment applications include from 0.5% to 99.9%, especially from 1% to 95%, of the desired ingredients, and from 99.5% to 0.1%, especially from 99% to 5% solids or liquids. Agents (including, for example, solvents such as water), wherein the adjuvants can be surfactants, the amount being from 0% to 50%, especially from 0.5% to 40%, based on the premix formulation.

Typically, the formulation will comprise from 0.01% to 90% by weight of active ingredient, from 0% to 20% of an agriculturally acceptable surfactant and from 10% to 99.99% of a solid or liquid formulation of inert agent and one or more An adjuvant consisting of a compound having at least a compound of formula (I) and component B, and optionally other active agents, in particular a microbicide or preservative or the like. The concentrated form of the composition typically comprises between about 2% and 80% by weight, preferably between about 5% and 70% by weight of active agent. The form of administration of the formulation may, for example, comprise from 0.01% to 20%, preferably from 0.01% to 5%, by weight of active agent. While commercial products will preferably be formulated as a concentrate, the end user will typically use a diluted formulation.

Example

There is a synergistic effect, whenever the combination of active ingredients is greater than the sum of the effects of the individual components.

For a given combination of active ingredients, the expected effect E is subject to the so-called Colby (COLBY) formula and can be calculated as follows (COLBY, SR, "Calculating synergistic and antagonistic responses" ("Calculating synergistic and antagonistic responses" Of herbicide combination"), Weeds, Vol. 15, pp. 20-22; 1967):

Ppm = milligrams of active ingredient (=a.i.) per liter of spray mixture

X = % effect of active ingredient using p ppm based on active ingredient A)

Y = % effect based on active ingredient B) using q ppm of active ingredient.

According to Colby (COLBY), the active ingredient of p+q ppm, the expected (additive) active ingredient A) + B)

If the actually observed (O) effect is greater than the expected effect (E), then the effect of the combination is super-additive, ie there is a synergistic effect. In mathematical terms this synergy factor SF corresponds to O/E. In agricultural practices SF of .2 represents a significant improvement in the purely complementary accumulation of multiple activities (expected activity), while in customary practice The SF of .9 represents the loss of activity compared to the expected activity.

Tables 45 to 82 show the mixtures and compositions T1.055, T1.058 and T1iii.055 of the present invention, demonstrating control of a wide range of pests. Because the percentage of mortality cannot exceed 100%, only when separate active ingredient components are provided separately to provide control well below 100% The unpredictable increase in insecticidal activity is maximized when the ratio is applied. The synergistic effect may not be apparent when the individual active ingredient components have a low application rate with some slight activity. However, in some instances, the combination was observed to have high activity, with individual active ingredients being substantially inactive at the same application rate alone.

Myzus persicae (green peach aphid)

Feeding/residual contact activity, prevention

Sunflower leaf discs were placed on agar of 24-well microtiter plates and sprayed with DMSO test solution. After drying, the leaf discs were infested with a population of mixed age aphids. After 6 days of incubation (days after treatment), samples were examined for mortality. (1 PPM=1 mg l ^-1 )

Table 45

Table 46

Table 47

Table 48

Table 49

Table 50

Table 51

Table 52

Table 53

Table 54

Table 55

Table 56

Table 57

Table 58

Table 59

Table 60

Table 61

Table 62

Table 63

Table 64

Table 65

Table 66

Table 67

Table 68

Table 69

Table 70

Two-spotted spider mites (two-spotted spider mites):

Feeding/contact activity, prevention

The DMSO test solution was sprayed onto the legume leaf disc on agar in a 24-well microtiter plate. After drying, the leaf discs were infested with a mixed age group of cockroaches. Eight days later, the leaf discs were examined for mortality based on the mobile stage. (1 PPM=1 mg l ^-1 )

Table 71

Table 72

Table 73

Table 74

Table 75

Table 76

Table 77

Table 78

Table 79

Table 80

Table 81

Table 82

Table 83

Table 84

Table 85

Table 86

Table 87

Table 88

Table 89

Table 90

Table 91

Table 92

Table 93

Table 94

Table 95

Table 96

Table 97

Table 98

Claims (12)

A pesticidal mixture comprising a mixture of component (A) and component (B) as an active ingredient, wherein component (A) is a compound of formula (I) Where Q is (i) X, Y and Z are each independently C _1-4 alkyl, C _1-4 haloalkyl, C _1-4 alkoxy, C _1-4 haloalkoxy or halogen; m and n are independently of each other 0, 1, 2 or 3 and m+n is 0, 1, 2 or 3; G is hydrogen, metal, ammonium, ruthenium or selected from -C(=O)-R ^a and -C(=O)-OR a latent group of ^b , wherein R ^a is selected from the group consisting of hydrogen, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₂ -C ₁₂ alkynyl, C ₁ -C ₁₀ haloalkyl, and R ^b Is selected from C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₂ -C ₁₂ alkynyl and C ₁ -C ₁₀ haloalkyl; R hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl; and A is a C _1-4 alkyl group; or an agrochemically acceptable salt or N-oxide thereof; and component (B) is selected from at least one of the following: a) A macrolide selected from the group consisting of abamectin, emamectin benzoate, and spinetoram; b). Pyrmetrozine; c). pyrethroid selected from the group consisting of cyhalothrin, lambda-cyhalothrin, gamma - cyhalothrin; d) a diamine selected from the group consisting of The group consists of: chlorantraniliprole and cyantraniliprole; e) thiamethoxam; f) sulfoxaflor; g) The cyenopyrafen wherein the weight ratio of component A to component B ranges from 250:1 to 1:66. The pesticidal mixture of claim 1, wherein in the compound of formula (I), R is selected from the group consisting of hydrogen, methyl, ethyl, iso Propyl, n-propyl, tert-butyl, secondary butyl, isobutyl and n-butyl. The pesticidal mixture of claim 1 or 2, wherein in the compound of formula (I), the X, Y and Z series are independently selected from the group consisting of the following: Methyl, ethyl, isopropyl, n-propyl, methoxy, fluoro, bromo and chloro, and m+n is 1, 2 or 3. The pesticidal mixture of claim 1 or 2, wherein in the compound of formula (I), Q system (i) and A is selected from the group consisting of: Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tert-butyl. The pesticidal mixture according to claim 1 or 2, wherein Q system (i), m is 1, n is 1, X is methyl, Y is in the ortho position and is methyl, Z is in the pair The position is also chlorine, G-(C=O)CO-CH ₂ CH ₃ , A-methyl and R-methyl. The pesticidal mixture according to claim 1 or 2, wherein Q system (i), m is 1, n is 1, X is methyl, Y is in the ortho position and is methyl, Z is in the pair The position is also a methyl group, G is -(C=O)CO-CH ₂ CH ₃ , A is a methyl group and R is a methyl group. The pesticidal mixture of claim 1 or 2, wherein component B is selected from the group consisting of: cyhalothrin, lambda-cyhalothrin, gamma-trichlorofluorocyanate Pyrethroid, abamectin, imammin, thiamethoxam, pyridazine, flufenidil, ethyl spinosyn, chlorantraniliprole and cyanamide. The pesticidal mixture of claim 1 or 2, wherein the mixture comprises an agriculturally acceptable carrier and optionally a surfactant. The pesticidal mixture of claim 1 or 2, wherein the mixture comprises a formulation adjuvant. The pesticidal mixture of claim 1, wherein component (B) is selected from the group consisting of only one of a) to g). A method of controlling an insect, a mites, a nematode or a mollusc, the method comprising administering to a pest, a pest, or a plant susceptible to pest attack, as claimed in any one of claims 1 to 10. A defined mixture. A seed comprising a mixture as defined in any one of claims 1 to 10.